Process for breaking petroleum emulsions



Patented Mar. 18, 1947 PROCESS FOR BREAKING PETROLEUM I EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing. Application July 13, 1945,

Serial No. 604,990

8 Claims.

This invention relates to the resolution of petroleum emulsions.

One object of my invention is to provide a novel process for resolving petroleum emulsions of the Water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc, and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts from pipeline oil.

And still another object of my invention is to provide a new demulsifier for petroleum emulsions of the water-in-oil type.

Demulsification. as contemplated in the present application includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion, in absence oi such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

The demulsifying agent used in my herein described process for resolving petroleum emulsions, consists of a partial or fractional ester derived by reaction between a polycarboxy acid or anhydride, such as phthalic acid, and the dimer of what may be most conveniently referred to as 9,11-lin010: diricinolein. The conventional dehydration of castor oil or ricinoleic acid, or some other ester, results in the formation of a diene acid with the probability that two reactions ordinarily go to approximately the same degree. These reactions may be illustrated in the following manner:

(9,12-1inoleic acid) REACTION 2 HH H Iii H (9,1l-linoleic acid) United States Patents which illustrate this procedure are: Patents Nos. 2,140,271, dated Dec. 13, 1938, to Schwarcman; 2,195,225, dated Mar. 26, 1940, to Priester; 2,209,065, dated July 23, 1940, to Pelikan; 2,212,385, dated Aug. 20, 1940, to Brod; 2,225,830, dated Dec. 31, 1940, to Priester; 2,226.831, dated Dec. 31, 1940, to Priester; 2,246,768, dated June 24, 1941, to Ubben; 2,261,663, dated Nov. 3, 1941, to Rheineck; 2,336,186, dated Dec. '7, 1943, to Nessler; and 2,351,444, dated. June 13, 1944, to Miller.

The mixed isomers may be treated so as to convert the unconjugated isomer into the conjugated isomer. This isomerization reaction may be indicated thus:

HHH

(9,12-1inoleic acid) HH H Pill H (9,1l-linoleic acid) U. S. Patents exemplifying isomerization procedure of the kind indicated, are the following: Nos. 2,185,414, dated Jan. 2, 1940, to McKinney; 2,242,230, dated May 20, 1941, to Burr; and 2,350,583, dated June 6, 1944, to Bradley.

9 ll-linoleic acid of approximately to purity is obtainable in the open market and also available in the form of the ethyl or methyl ester.

Ignoring matters of cost, I prefer to prepare the monomeric mixed glyceride from this particular product. Methyl or ethyl ricinoleate, which can be prepared in the usual manner or purchased in the open market, is reacted in the customary manner with glycerol monochlorhydrin, using two moles of the ester for one mole of the chlorohydrin. The reaction may be indicated thus:

CuHuOHC O CnHazOHC O CnHazOHCOO l I osmgol NaEO 0.617133! CnHazOHCOO Other alternate procedures may be used, and particularly some in which the percentage of mixed glyceride is not as high in the product obtained by the described procedure, but still sufiiciently high for the manufacture of valuable products for the employment of processes herein described.

In regard to the above esterificatlon procedure or alternate procedure, see the comprehensive article entitled Polyhydric alcohol esters of fatty acids," in Chemical Reviews, volume 3, No. 3, at page 257.

The polymerization of the diene acid is conducted in the same identical manner employed for the polymerization of the methyl ester. The polymerization of the methyl ester is described in various U. S. Patents, as, for example: Nos. 2,325,040, dated July 27, 1943, to Cook et al.; 2,347,562, dated Aug. 25, 1944, to Johnston; and 2,357,839, dated Sept. 12, 1944, to Evans et al.

The dimerization of the methyl ester may be indicated in the following manner:

2 moles methyl ester 9,11-octadecadienic acid (originally present and/or formed by isomerization of 9,12 isomer) (CHzhC-OCH:

t t Ho oc=0(om)1c-ocm HI") HC-(CH2)5CH: O

(See U. S. Patent No. 2,347,562, April 25, 1944, to Johnston, above mentioned.)

In polymerization of polyene acid esters it has been found that temperatures between about 250 C. and about 350 C. are suitable for the polymerto one hour at about 300 0., whereas, the methyl linolenates and linoleates generally require from about 5 to 12 hours or more. To speed up the polymerization process, suitable catalysts may be added, examples of which are: fullers earth (preferably acid-treated), bentonite (preferably acid-treated), stannic chloride, etc. If catalysts be employed, it is sometimes possible to use lower temperatures and/or shorter periods of time than those indicated above. Substantially the same conditions may be used for dimerization, provided however, that they must be below the point where dehydration of the ricino-leic acid radical takes place. In other words, in the present instance the upper temperature of limit is approximately 250 C., and as a result of a somewhat lower temperature, it is sometimes desirable to use a longer time period for isomerization, for instance, a time period as long as twenty-four to forty-eight hours.

Other means for inducing or hastening or catalyzin polymerization of the above described reactants are well known. See, for example, U. S. Patent No. 2,207,686, dated July 9, 1940, to Schwarcman.

In any event, any suitable procedure is used to prepare the mixed glyceride which has the following formula:

Said mixed glyceride is then dimerized in the manner previously described to produce the dimer of the following formula:

An examination of the preceding formula immediately suggests additional procedures for producing the dimer of the mixed glyceride. For instance, a raw material which can be readily prepared or purchased in the open market, is diricinolein. The formula for such product, ignoring isomeric forms, is, of course:

H 'CHa(CH2)5CHOHCHaCH=CH(CH2)7CO O CH It becomes obvious that if two moles of diricinolein could be reacted with one mole of the dimeric acid which has been previously depicted in the form of a methyl ester, one would then obtain the ;d;imerizedmixed glyceride preyiously described.

involve the ricinoleyl hydroxyl radical. Thus, such procedure, although giving fair yields, also gives admixture with other products which preferably are avoided. However, if the methyl ester or ethyl ester of the dimeric acid is used so esterification involves the elimination of the methyl or ethyl alcohol, then and in that event, the reaction appears to be limited largely to involving the glycerol hydroxyl.

Another procedure which immediately suggests itself in the formation of the monomeric mixed glyceride, is the procedure commonly referred to as re-esterification, cross-esterification, or transesterification. Such procedure is well known, and in essence, would involve, for example, mixing two moles of triricinolein with one mole of the total or complete glyceride of 9,11-linoleic acid dimer. Such migration of the acyl radicals takes place at a temperature below the pyroiytic point of triricinolein, and in presence of an alkaline catalyst. The suitable. temperature is approximately 250 C., or slightly less, and the time required may be comparatively long, for instance, 36 to '72 hours.

In any event, one obtains the dimerized mixed glyceride by any suitable procedure, and the product employed should preferably contain at 'least 65% or more of the dimerized mixed glyceride; some of the procedures above enumerated will yield a product markedly in excess of this value. Such mixed glyceride, if carefully prepared, has a viscosity approximately that of castor oil, or slightly blown castor oil, a distinctly darker color, and perhaps, a less pleasant odor. The chemical weight, iodine number, hydroxyl number and saponification value, approximate the calculated theoretical value. It is to be noted that this intermediate is not claimed herein per se.

Such dimerized mixed glyceride previously described in detail, is subjected to reaction with polybasic carboxy acids.

Polybasic carboxy acids which may be employed in the esteriiication reaction may be exemplified by phthalic, succinic, malic, fumaric, citric, citraconic, tricarballylic, maleic, adipic, tartaric, oxalic, or the like. The anhydrides of such polybasic carboxy acids, such as phthalic anhydride, maleic anhydride, etc., are the equivalents of the acids, and in some respects, are even more advantageous than the acids in the production of esters. When reference is made to polybasic carboxy acids, the anhydrides thereof are also included. Other suitable polybasic acids may be prepared by the diene synthesis which involves condensation of alpha-beta, unsaturated acids or anhydrides with compounds containing a conjugated double bond. For example, the condensation of maleic anhydride with alpha-terpinene yields a dicarboxy acid which is suitable. Other polybasic carboxy acids may be prepared similarly by the diene synthesis involving condensation of an alpha-beta, unsaturated monocarboxy acid With a carboxy acid containing a conjugated double bond. For example, crotonic acid may be condensed with abietic acid, which contains a conjugated double bond, to yield a dicarboxy acid suitable for use in the manufacture of the herein contemplated products.

It has been found, however, that of all the acids available, the dicarboxy acids having six carbon atoms or less are articularly preferable. The

choice is to use such acids which are cheap and particularly resistant to pyrolysis, such as phthalic acid or the anhydride, maleic acid or constants, such as molecular the anhydride, citraconic acid or the anhydride, and adipic acid. It is known, of course, that if a dimer of the kind above described is heated with maleic anhydride or the like, or some other dienophile, that a more complicated series of reactions will take place, and this, as a matter of fact, would apply even if the ricinoleyl radical were replaced by an oleyl radical. The present invention is not concerned with this particular variant. Indeed, maleic acid may even add under appropriate conditions to the double bond which has been shown as part of a cyclic structure in a previous representation of the structural formula of the dimerized mixed glyceride.

For convenience then, rather than repeat the above structure, which is rather burdensome, it is sumcient to present a simpler form which may be represented thus:

HORCOOEZ H HORCOOCH OH HORCOOJIH HORCOOOH Such formula shows clearly that the dimerized mixed glyceride may serve as a tetrahydric alcohol of fairly high molecular weight and that it may be subjected to reaction in the same way that castor oil, which may be considered a trihydric alcohol, is esterified with various polycarboxy acids, particularly phthalic anhydride, maleic anhydride, citraconic anhydride, and adipic acid. The procedure of reacting castor oil or similar polyhydroxy alcohol esters of hydroxylated fatty acids requires no elaboration. Briefly stated, one pound mole of the dimerized mixed glyceride, for instance, one pound mole of dimeric 9,1l-linolo-diricinolein, is mixed with a predetermined amount of the selected polycarboxy acid, for instance, one mole, two moles, three moles, or somewhat less than four moles. The reaction is conducted at any suitable temperature above C. and below the pyrolytic point of either the ricinoleyl radical, or of the polycarboxy acid selected. Insofar that one can employ any number of polycarboxy acids which are resistant to pyrolysis from a practical standpoint, one need only employ a, temperature below the pyrolysis of the ricinoleyl radical, that is, a temperature of approximately 250 C., or slightly less. Such reaction mass is stirred constantly during reaction, and if desired, a very small quantity of a. dried inert gas, such as nitrogen, is passed through during the course of reaction. The objection to such procedure is only that if the polycarboxy reactant sublimes, as in the case of phthalic anhydride, some may be lost. There is no need to add the usual esterification catalyst, such as one-tenth to five-tenths of 1% of toluene sulfonic acid, but if added, it appears to hasten the reaction. The time of reaction varies, but approximately six to fifteen hours will serve. The mass should be stirred continuously during reaction. If no inert gas is passed in the mass, then any phthalic anhydride or the like which sublimes, can be scraped from the condenser by a continuous scraper and returned to the reaction mass. Completeness of the reaction can usually be determined by the fact that the cooled reaction mass stays clear, indicating the absence of any reactive polycarboxy acid or anhydride. In any event, a representative sample can be taken and titrated so as to determine the acid value, and it is to be noted that at the end of the reaction, the acid value should approximately indicate that onehalf of the dicarboxy acid carboxyls have reacted. The entire process is to produce a fractional or partial ester having at least one and preferably more free carboxyl radicals. \AS previously pointed out, a simple determination of the acid value denoting the percentage of unreacted carboxyl radicals in the mechanical mixture at the beginning of the reaction and in the chemical compound at the end of the reaction, will serve. To some degree, it is possible that there is some linkage wherein one mole of the polycarboxy reactant involves two moles of the dimer. However, molecular weight determinations on the finished product appear to indicate that there is comparatively a small fraction, if any, of a subresinous material involving the po-lyfunctionality of both the dimerized mixed glyceride and the dicarboxy acid. Obviously, the likelihood for such higher polymer formation increases as the molal ratio of the polycarboxy reactant increases, and other factors come into play, such as higher temperature of reaction, increased time of reaction, etc. This conforms to expectations.

The preferred composition represents such compounds as dimeric 9,11-1inolo-diricinolein mono-acidphthalate, 9,11-linolo-diricinolein diacidphthalate, and similarly, the tri-acidphthalate, and mixtures of the tri-acidphthalat and the tetra-acidphthalate. Of equal interest are the corresponding acid maleates, corresponding acid adipates, and corresponding acid citraconates and succinatcs. Although further description is unnecessary, it is to be noted that in subsequent examples some of the preferred products are exemplified by illustration and structural formulae which are not intended to refer to any particular isomer.

Example 1 One pound mole of dimerized 9,11-linolo-diricinolein is reacted with one pound mole of phthalic anhydride.

: E 002011 HEORCOQCE "'nonooon on on HOROOOCH noncooon For convenience of depicting the acid, phthalic acid is shown instead of the anhydride. The significance of R1 has been indicated previously. The procedural steps are those previously indicated, but briefly, require nothing more or less than reaction for approximately two to six hours with constant stirring at about 225 C. to 250 C.

Acatalyst may be added, such as one-fourth of 1% of toluene sulfonic acid, or dried carbon dioxide maybe passed through the mixture, provided that safeguards are taken not to lose phthalic anhydride by sublimation.

Example 2 Two moles of phthalic anhydride are employed for each mole of the dimer. The conditions of reaction are substantially the same as previously indicated.

ooion nionooo n nonooocn on HORCOOt lH on HioRooooH Example 3 The molar proportion of phthalic anhydride is increased so as to introduce approximately 3 /2 moles of phthalic anhydride per mole or dimer.

Example 4 Adipic acid is used instead of phthalic anhydride in Examples 1 to 3, preceding.

Example 5 Succinic acid is used instead of phthalic anhydride in Examples 1 to 3, preceding.

Example 6 preference is simply that as more drastic condi-' tions are employed, particularly for introduction of higher molal amounts of the dicarboxy acid, maleic acid or the anhydride, or citraconic acid, or the anhydride, may undergo polymerizations by addition or rearrangement, as distinguished from conditions which normally eliminate water or some other small molecule, provided that such reactant employing a carboxyl is used. If, however, the reactions are conducted cautiously so as to avoid any undue complications, one obtains products of equal value from such materials as maleic anhydride, or citraconic anhydride.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as gasoline, kerosene, stove oil; a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demul'sifying agents. Moreover, said material or materials may be used alone, or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and Water solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, in desalting practice, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

I desire to point out that the superiority of the reagent or demulsifying agent employed in my process, is based upon its ability to treat certain emulsions more advantageously and. at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majortiy of oil field emulsions are concerned; but I have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practicing my process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agentrof the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to the emergence of said fluids. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

One preferred and more narrow aspect of my invention, insofar as it is concerned with demulsification of petroleum emulsions of the water-in-oil type, is concerned with the admixture of the esters, as described, with a viscosity-reducing solvent, such as the various solvents enumerated, particularly aromatic solvents, alcohols, ether alcohols, etc., as previously specified. The word solvent is used in this sense to refer to the mixture, if more than one solvent is employed, and generally speaking, it is my preference to employ the demulsifier in a form representing 40% to 85% demulsifier and 15% to 60% solvent, largely, if not entirely, non-aqueous and so selected to give a solution or mixture particularly adaptable for proportional pumps or other measuring devices. The following exam ples will illustrate this aspect of my invention:

DEMULSIFIER Example 1 Per cent Partial ester, as exemplified by acid ester,

Example 1 Xylene 20 Isopropyl alcohol 20 DEMULSIFIER' Example 2' Per cent Partial ester, as per acid ester, Example 2, derived from reactants in molal ratio of (The above proportions represent percentage by weight.)

I am aware that valuable products suitable for use in demulsification, may be prepared by considering the acidic fractional esters herein contemplated as intermediates. Such intermediates can be subjected to oxyethylation with ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, so as to give watersoluble products. Similarly, such intermediates may be reacted with hydroxylated tertiary amines, particularly triethanolamines, to give acylated derivatives having particularly valuable properties for the purposes enumerated in the present paragraph.

Attention is directed to the fact that the compounds herein contemplated, although derived essentially from one mole of the dimer, may actually represent subresinous materials, in which two or three moles of the dimer are joined by a polycarboxy acid radical. It becomes obviously difiicult, if not impossible, to present a formula depicting such more elaborate and more complicated aspect of the invention. However, in regard to the simpler aspect, that is, derivatives of the dimer, it is to be noted that structural formulae present an adequate portrayal.

As has been previously pointed out, the mixed ester herein contemplated for dimerization is referred to as 9,11-1inolo-ricinolein. This nomenclature appears to conform with that commonly employed in designation of mixed glycerides having one linoleyl radical, although from more formal nomenclature, it is possible that the expression 9,1l-linoleyl-diricinolein would be appropriate, since in essence a hydrogen atom of diricinolein has been replaced by the 9,1l-linoleyl radical.

Previous reference has been made to the fact that the preferred form of the present composition, when used for demulsification, involves admixture with viscosity-reducing solvents, as exemplified by Demulsifier, Examples 1 to 3, preceding. It may be well to emphasize the fact that in such examples the partial ester is both oil and water-insoluble, and this characterizes one property of the most desirable mixtures with solvents, i. e., that the partial ester employed for admixture with the solvent be both oil and waterinsoluble within the ordinary meaning.

The new chemical products or compounds aeimas 11 herein described forms theT'subject-matter of my divisional application Serial No. 707,977, filed November 5, 1946.

Having thus described my invention, what I claim as new and desire to secure by Letters Patentis:

1 A process for breaking petroleum emulsions of the water-in-oil type, characterizedby subjecting the emulsion to the action of an acidic partial ester derived by reaction between a polycarboxy acid and dimerized 9,11-linolodiricinolein.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjectingthe emulsion to the'action of an acidic partial ester derived by reaction between a dicarboxy acid and dimerized 9,11-linolo-diricinolein.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of an acidic partial ester derived by reaction between a dicarboxy acid having less than 9 carbon atoms, and dimerized 9,1l-linolo-diricinolein.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of'an ester in which at least one ricinoleyl hydroxyl hydrogen atom of has been replaced by the radical-OCRzCOOI-I of a dicarboxy acid of the formula HO.OCR2COOH having less than 9 carbon atoms, in which R2 is the divalent carboXy1free residue of said dicarboxy acid.

has been replaced by the radical-OCRzCOOH of a dicarboxy acid of the formula HO.OCR2COOH having less than 9 carbon atoms, in which R2 is the divalent carboxyl-free residue of said dicarboxy acid.

6. A process of claim 5, wherein HO.OCR2COOH is phthalic acid.

7. The process of claim 5, wherein HO.OCR2COOH is adiptic acid.

8. The process of claim 5, wherein HO.OCR2COOH is diglycollic acid.

IWELVIN DE GROOTE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,310,395 Carruthers Feb. 9, 1943 2,363,506 De Groote et a1. Nov. 28, 1944 2,000,717

Roberts May 7, 1935 

